CN1033651A - The tungsten ferronickel heavy alloy and the production method thereof of very high mechanical properties - Google Patents

The tungsten ferronickel heavy alloy and the production method thereof of very high mechanical properties Download PDF

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CN1033651A
CN1033651A CN88107568A CN88107568A CN1033651A CN 1033651 A CN1033651 A CN 1033651A CN 88107568 A CN88107568 A CN 88107568A CN 88107568 A CN88107568 A CN 88107568A CN 1033651 A CN1033651 A CN 1033651A
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居伊·尼古拉
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Cime Bocuze SA
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/045Alloys based on refractory metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04Alloys based on tungsten or molybdenum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18High-melting or refractory metals or alloys based thereon

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Abstract

The present invention relates to mechanical property high tungsten ferronickel heavy alloy and production method thereof.
This alloy is characterised in that tungsten α is butterfly wing shape mutually, and the dislocation unit cell dimension is 0.01-1 μ m, and γ is in conjunction with the mean free path that has mutually less than 15 μ m.
This method comprises, makes through sintering and heating product and stands three operational cycles at least, and each cycle heat-treats after being included in process operation.
It is 1300-2000MPa that the present invention can be used for the anti-grain of manufacturing limit intensity, and the special alloy that uses under the situation of high-load level very comprising prepared.

Description

The tungsten ferronickel heavy alloy and the production method thereof of very high mechanical properties
The present invention relates to the tungsten ferronickel heavy alloy and the production method thereof of very high mechanical properties.
The professional of this technical field is known, is intended to be used for making counterweight, absorption of vibrations screen and X, α, β, gamma-rays absorbing screen, and high-penetration ability De Gun bullet, and its material must have sizable density.
Given this cause, producing these things will be by means of the alloy of so-called " weight " alloy.Such alloy mainly contains tungsten, and the tungsten homogeneous is dispersed in usually by in conjunction with element, for example in the formed metallic matrix of nickel and iron.In most of the cases, this class alloy contains the 90-98%(weight ratio) tungsten, proportion is 15.6-18.Such alloy is mainly made with powder metallurgic method, be that its each component is all used with pulverulence, and be pressed into suitable shape, sintering and stabilization, to give its mechanical density, and may stand processing and thermal treatment, so that it has the mechanical property that is fit to its purposes: intensity, unit elongation and hardness.
The technical specifications of such alloy for instance, has been made regulation in United States Patent (USP) NO.3979234, this patents state a kind of method of producing the W-Ni-Fe alloy, comprising:
A kind of 85-96%(weight ratio that contains of-preparation) tungsten, surplus is that nickel and iron and Ni/Fe weight ratio are the powder uniform mixture of 5.5-8.2,
-this mixture is pressed into the rolled-up stock shape,
-in reducing atmosphere at least 1200 ℃, and be lower than the sufficiently long time of the sintering temperature that liquid phase occurs, producing the product that a kind of density is at least theoretical density 95%,
-product is produced under the temperature of temperature 0.1 between with 20 ℃ being higher than liquid phase, heat one section be enough to make the liquid phase generation and deficiency so that the time that product is out of shape,
-with product in a vacuum in 700-1420 ℃ the heating the enough time, make it the degassing, and
-product is machined to desired size, this operation can be carried out to improve product strength through processing together at least.
Resulting under these conditions, be a kind of product for example, it makes after surface-area reduces by 31% processing operation a kind of, and ultimate tensile strength RM is 1220MPa, yield strength R 0.2Be 1180MPa, unit elongation E is 7.8%, and Rockwell C level hardness is HRc41.These character are enough to be fit to some purposes, but for the high purposes of load level, this is obviously not enough, because be greater than 1600MPa to the requirement of ultimate tensile strength grade at present, and can be up to 2000MPa.
The present invention relates to a class heavy alloy, its proportion is between 15.6 and 18, contain the 80-99%(weight ratio) tungsten and nickel, iron (the Ni/Fe weight ratio is more than or equal to 1.5), and optionally contain other element such as molybdenum, titanium, aluminium, manganese, cobalt and rhenium, such alloy has high mechanical property, especially the paramount 2000Pa that reaches of ultimate tensile strength, unit elongation is at least 1%.
This class alloy of the present invention is characterized in that α is the butterfly aliform mutually in its tissue, and the dislocation unit cell dimension is 0.01-1 μ m, and the mean free path of wedding agent γ phase is less than 15 μ m.
The professional in present technique field is known, tungsten-nickel-ferro-alloy has a kind of by the formed tissue of pure tungsten ball-joint, and ball-joint nodularization more or less in sintering circuit constitutes the α phase, the γ that this ball-joint is made up of the element of this alloy surrounds mutually, and γ plays keying action between ball-joint.
The applicant finds that will reach high mechanical property, tungstenalloy must have special knitting.
Therefore, from morphologic angle, if observation can be found perpendicular to the surface of machine direction on the sample that is made by this class alloy:
-α no longer is the shape of nodularization mutually, and is the Elliptical sphere slightly, and links together in pairs near an end of major axis, acutangulates between major axis, and above-mentioned arrangement is called as " butterfly wing " more at large, and
-especially reduce in conjunction with the mean free path of γ phase with the raising of ultimate tensile strength proportionally.Therefore, mean free path is during less than 15 μ m, and ultimate tensile strength reaches more than the 1600MPa.
Mean free path one speech used herein means and separates two mean distances of γ phase region in turn on the certain orientation.
From the angle of microstructure, if get thin mushroom sheet, can find to have the dislocation structure cell existence that is of a size of 0.01-1 μ m in mutually at α, it reduces with the raising of the mechanical property of materials proportionally.Consistent with the raising of the mechanical property of materials, relative disorientation also was observed between structure cell was mutual, it is believed that those structure cells make such alloy have necessary plasticity of when deforming just.In addition, be parallel to the observation of being carried out on the sample of machine direction on the surface and also disclosed the proportional more tangible fiber texture that becomes with mechanical performance raising.Above-mentioned fiber is a feature with its specific orientation, and this kind orientation is by Miller's indices, is equivalent to<110〉direction for the limit { 110 } of sample central part
Yet the raising of mechanical property surpasses the polygonization that the α phase can take place the 1500MPa level.As incidental situation, the net of separating out of relevant γ phase develops in α phase ball-joint neighboring region.
The invention still further relates to a kind of method of producing alloy, the alloy of being produced has a kind of like this tissue, can regulate required mechanical behavior value on demand in this tissue, especially can make breaking tenacity near 2000MPa.
For reaching top described, consider that α enbrittles mutually usually, but the elastic limit height, the applicant has improved the processing of such alloy, makes it to promote the viscous deformation of α phase.
This method comprises known processing step and is made up of the following step:
-using the powder of each alloying element, every kind of powder all has the FISHER diameter of 1-15 μ m,
-above-mentioned powder is mixed with the ratio that is equivalent to required alloy composition,
-above-mentioned powdered mixture is pressed into the shape of rolled-up stock,
-under 1490-1650 ℃ with rolled-up stock sintering 2-5 hour,
-handle the rolled-up stock that sintering is crossed in 1000-1300 ℃ in a vacuum, and
-make resulting rolled-up stock stand one processing at least.
But what characterize this method is, after vacuum-treat, rolled-up stock stands at least three operational cycles, and each cycle comprises a procedure of processing and back with thermal treatment.
Therefore, the present invention was made up of the cycle in turn, and number of cycles increases with organize pro rata suitable with relevant mechanical property maximum that will obtain.Thereby three circulations can make its ultimate tensile strength level that reaches 1400-1450MPa, and when four loop ends, reach the value near 1850MPa.Each circulation comprises a procedure of processing successively, the procedure of processing of carrying out for example with forging method, so that the degree that reduces of sintering rolled-up stock surface-area is improved 10-50%, and be lower than 1300 ℃ stove with rolled-up stock being put into to be heated to after it, in inert atmosphere, continue the annealing of being carried out in 4-20 hour.
In beginning two cycles, with processing stage less than the back with the cycle temperature to be higher than the back be good with the cycle.In the 4th cycle, for example before heat-treating, in forging equipment, carry out the processing of successive twice at least, to reach suitable degree of finish.
The present invention can illustrate with accompanying drawing, relates to a kind of 93%(of containing weight in the accompanying drawing) tungsten 5%(weight) nickel and 2%(weight) alloy of iron, wherein:
Fig. 1,2 and 3 illustrates the tissue of sample cross when amplifying 200 times that has ultimate tensile strength 1100,1540 and 1850MPa respectively.
When Fig. 4,5 and 6 illustrates the tensile strength that is obtained by same sample, the displaing micro tissue topography when relevant fracture amplifies 1000,1000 and 2600 times respectively, and
Fig. 7,8 and 9 illustrates and amplifies 35000,30000 and 60000 times of thin being seen microstructures of abrasive disc of observation under the electron microscope respectively, has shown to make it may reach the particular state of the α phase of desired properties.
Fig. 1 shows the globular structure of white tungsten α phase, and mean free path near 20 μ m in conjunction with the γ phase.
Fig. 2 illustrates and forms the butterfly wing when mean free path is reduced to about 10-14 μ m.
Among Fig. 3, strengthen in trend seen in fig. 2, mean free path is in the 3-7 mu m range.
Among Fig. 4, alloy fracture occurs between ball-joint and γ top (CuPular) mutually basically.
Sample among Fig. 5 and 6 has higher mechanical property than person shown in Fig. 4, can see, whole fracture pattern becomes wears ball-joint (transnodular).Accidental have the fracture between ball-joint initial.In α phase microstructure scope, the substructure state develops to some extent.
Fig. 7 illustrates the structure cell that rearranges that is of a size of 0.4-0.8 μ m and restores tissue.
Fig. 8 illustrates the polygonization step, and this step is that to reach peak performance necessary.
Fig. 9 illustrates the typical organization of peak performance, with the dislocation crystallite born of the same parents development of 0.05-0.01 μ m.
The present invention can illustrate with reference to the embodiment of following this method of use:
With the FISHER diameter is that each elementary state powder of 1.4-10 μ m is mixed, to make the product (weight ratio) with following composition: W93%-Ni5%-Fe2%.
Through after the compacting of the inferior static pressure of 230MPa pressure, with the rolled-up stock of diameter 90mm, long 500mm in continuous tunnel furnace in 1490 ℃ of sintering temperatures 5 hours, maintenance 25 hours in being heated to 900-1300 ℃ stove in partial vacuum then.
The product that makes is like this handled by of the present invention again.The specified conditions that period treatment is carried out, and the mechanical property Rm(ultimate tensile strength that is reached in the cycle in different treatment), R0,2(unit elongation be 0.2% yield strength), the E(unit elongation), the VH30(Vickers' hardness) and the RHc(Rockwell hardness) be listed in the table below:
Figure 88107568X_IMG1
Therefore as seen, breaking tenacity improved greatly when cycle life increased, and unit elongation keeps to such an extent that enough allow alloy deformation.

Claims (7)

1, the high heavy alloy of mechanical property, its proportion is 15.6-18, contain 80-99% (weight ratio) and constitute the ball-joint shape tungsten of α phase and Ni/Fe weight ratio more than or equal to 2 nickel and iron, nickel plays keying action and constitutes γ mutually with iron, and can contain selective element such as molybdenum, titanium, aluminium, manganese, cobalt, reach rhenium, it is characterized in that tungsten α is butterfly wing shape mutually, its dislocation unit cell dimension is 0.01-1 μ m, and has mean free path less than 15 μ m mutually in conjunction with γ.
2, the described alloy of claim 1 is characterized in that, α has the fiber texture of<110〉direction mutually.
3, the described alloy of claim 1 is characterized in that, the ultimate tensile strength level is during greater than 1500MPa, α phase polygonization.
4, the described alloy of claim 1 is characterized in that, γ forms in adjacency α phase ball-joint district and separates out net.
5, the method for the described alloy of production claim 1 comprises:
The powder of each element of-use 1-15 μ mFISHER diameter,
-with described powder being equivalent to the mixed of required alloy composition,
-powder is pressed into the rolled-up stock shape,
-under 1490-1650 ℃ temperature with rolled-up stock sintering 2-5 hour,
-the rolled-up stock in a vacuum sintering crossed is handled down at 1000-1300 ℃, and
-make rolled-up stock stand one processing at least,
It is characterized in that rolled-up stock makes it stand three operational cycles at least after vacuum-treat, each cycle comprise a procedure of processing and the back with thermal treatment.
6, the described method of claim 5 is characterized in that, the beginning two cycles in, degree of finish less than the back with cycle, thermal treatment temp be higher than the back with cycle.
7, the described method of claim 6 is characterized in that, in the 4th cycle, process operation carries out twice at least.
CN88107568A 1987-10-23 1988-10-20 Heavy tungsten-nickel-iron alloys with very high mechanical characteristics and process for production of said alloys Expired CN1019318B (en)

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FR8715315A FR2622209B1 (en) 1987-10-23 1987-10-23 HEAVY DUTIES OF TUNGSTENE-NICKEL-IRON WITH VERY HIGH MECHANICAL CHARACTERISTICS AND METHOD OF MANUFACTURING SAID ALLOYS
FR8715315 1987-10-23

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CN107058841A (en) * 2017-06-29 2017-08-18 浙江创特新材科技有限公司 A kind of high mechanical properties tungsten alloy material and preparation method thereof
CN107848036A (en) * 2015-07-22 2018-03-27 康·伯克兹公司 The manufacture method of penetration device comprising the core surrounded by ductility sheath and this penetration device
CN109518054A (en) * 2019-01-15 2019-03-26 株洲市美力迪实业有限公司 A kind of broaching tool material and preparation method thereof and broaching tool

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CN107848036A (en) * 2015-07-22 2018-03-27 康·伯克兹公司 The manufacture method of penetration device comprising the core surrounded by ductility sheath and this penetration device
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CN107058841A (en) * 2017-06-29 2017-08-18 浙江创特新材科技有限公司 A kind of high mechanical properties tungsten alloy material and preparation method thereof
CN107058841B (en) * 2017-06-29 2018-12-21 浙江创特新材科技有限公司 A kind of high mechanical strength tungsten alloy material and preparation method thereof
CN109518054A (en) * 2019-01-15 2019-03-26 株洲市美力迪实业有限公司 A kind of broaching tool material and preparation method thereof and broaching tool

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